CN106007802A - Resin-permeable ceramic composite and preparation method thereof - Google Patents
Resin-permeable ceramic composite and preparation method thereof Download PDFInfo
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- CN106007802A CN106007802A CN201610349596.5A CN201610349596A CN106007802A CN 106007802 A CN106007802 A CN 106007802A CN 201610349596 A CN201610349596 A CN 201610349596A CN 106007802 A CN106007802 A CN 106007802A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/483—Polyacrylates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
Abstract
The invention provides a resin-permeable ceramic composite which is formed by curing a ceramic body and mixed resin permeating in the porous network structure of the ceramic body, wherein the ceramic body has a porous network structure and comprises yttria-stabilized tetragonal phase zirconia; and the mixed resin comprises a mixture of methacrylate compounds and a thermal curing agent. The resin-permeable ceramic composite provided by the invention is composed of a porous ceramic network structure and resin permeating in the ceramic network structure; by adopting the ceramic as a matrix, the volume change of the composite in the curing process can be effectively avoided, and the defects that traditional particle reinforcing resin-based composite is easily cured and shrunk and consequently residual stress is introduced are overcome; and through the permeation way, the mixed resin can form a resin network structure penetrating through the ceramic network structure, and a ceramic-based composite with excellent mechanical properties is obtained.
Description
Technical field
The invention belongs to gear division repair materials technical field, particularly relate to a kind of resin penetration ceramic composite and system thereof
Preparation Method.
Background technology
Oral cavity health is closely bound up with national life quality, and according to World Health Organization's recent statistics, oral disease is arranged
For the third-largest disease after cancer and cerebrovascular disease.Research display, the prevalence of the various oral pathology of China is up to
97.6%, it is concentrated mainly on the oral pathology such as dental caries and periodontitis.Third National oral health epidemiological survey result shows
China's population caries incidence is 40%, and each patient averagely relates to 2-3 tooth.Along with population structure aging and people are to life
The raising of prescription, demand and the research of Oral Repair treatment expand the most rapidly.It is presently used for the composite that gear division is repaired
Research defined a direction with important research and Practical significance, exploitation advanced composite material (ACM) and synthesis side simultaneously
The optimization of method is also current gear division repair materials research emphasis.
Ceramic material and composite combine CAD/CAM technology and are widely used in gear division reparation field in recent years.The most main
There are two classes for the ceramic material that gear division is repaired, respectively: glass ceramics and polycrystalline ceramics (Li R.W.K., et.al,
J.Prosthodont.Res.,2014,58,208-216)。
Glass ceramics, such as Lithium silicate glass pottery, although there is biocompatibility and the aesthetic properties of excellence, but
Fragility is big, and mechanical property is poor.And there is the polycrystalline ceramics of higher intensity and toughness, such as alumina-based ceramic or oxidation zirconio
Pottery, has defect opaque, that hardness is high and modulus is high.For gear division repair materials, opaque, mean aesthetic properties
Difference；In order to make up this defect, at top ceramic layer plus decorations porcelain, but porcelain poor mechanical property would generally be adornd during repairing
And poor with the binding ability of dummy, finally easily cause the inefficacy of whole dummy, the hardness of polycrystalline ceramics is typically
Adamantine 2-4 times, the repair materials of too high hardness will wear and tear the natural tooth of surrounding, damages natural tooth；
Secondly, in human teeth, Dentinal Young's modulus is 20-25GPa, well below zirconium oxide (200GPa) and aluminium oxide (340-
Young's modulus 390GPa), power transmission in repair materials and natural tooth will be caused negatively by this significant difference
Impact (Ziskind D., et.al, J.Struct.Biol., 2011,174,23-30；White S.N.,et.al,
J.Prosthet.Dent.,2005,94,125-131；Mangalaraja R.V.,et.al,Mater.Sci.Eng.A,2003,
343,71-73)。
In order to mechanical property preferably be combined with aesthetic properties, composite is introduced into gear division at 1960s and repaiies
Multiple field, and people are being devoted to improve their performance always after this.(Ferracane J.L.,et.al,
Dent.Mater., 2005,21,36-42) but, the intermolecular bond distance being far smaller than between monomer due to the bond distance of covalent bond,
Inorganic particle toughened resin based composites has significant shrinkage after hardening, and this distinctive shrinkage is compound
Material repair process can introduce residual stress, thus cause repair materials to depart from dummy, seriously limit resin base and be combined
The extensively application (Ferracane J.L., et.al, Dent.Mater., 2011,27,29-38) of material.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of resin penetration ceramic composite, the tree that the present invention provides
Fat osmotic ceramic composite is constituted with ceramic network structure and the infiltration resin in ceramic network structure of porous, overcomes
The shrinkage of conventional particles toughened resin based composites, it is easy to introduce the defect of residual stress.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides a kind of resin penetration ceramic composite, described composite is by ceramic body and permeates in institute
Stating the solidification of the hybrid resin in the porous network structure of ceramic body to form, described ceramic body has the network structure of porous,
Described ceramic body includes that the tetragonal phase zirconium oxide of stabilized with yttrium oxide, described hybrid resin include methyl acrylic ester compound
Mixture and thermal curing agents.
Preferably, described ceramic body also includes iron sesquioxide, in described ceramic body moles the hundred of iron sesquioxide
Proportion by subtraction is 0～3mol%.
Preferably, described thermal curing agents is benzoyl peroxide.
Preferably, the mixture of described methyl acrylic ester compound be bisphenol-A glycerine dimethacrylate, three
One or more in (ethylene glycol) dimethylacrylate, methacrylate and polymethyl methacrylate.
The invention provides the preparation method of a kind of resin penetration ceramic composite, comprise the following steps:
(1), it is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtain hybrid resin；
(2), the hybrid resin that described step (1) obtains is infiltrated in ceramic body, obtain being impregnated with the pottery of resin；
(3), the pottery being impregnated with resin that described step (2) obtains is solidified, obtain resin penetration Ceramic Composite
Material.
Preferably, the preparation method of described ceramic body comprises the following steps:
A, by the tetragonal phase zirconium oxide of stabilized with yttrium oxide pottery and iron sesquioxide mixing, obtain mixed material；
B, the mixed material that described step a obtains is ground, obtains presoma powder body；
C, the presoma powder body described step b obtained once are suppressed, and obtain biscuit of ceramics precursor；
D, the biscuit of ceramics precursor described step c obtained carry out secondary compacting, obtain biscuit of ceramics；
E, the biscuit of ceramics that described step d obtains is sintered, obtains ceramic body.
Preferably, in described hybrid resin, the mass fraction of thermal curing agents is 0.5～2%.
Preferably, the time of the infiltration described in step (2) is 2～24h.
Preferably, the environment of the infiltration described in step (2) is vacuum environment.
Preferably, the temperature of step (3) described solidification is 50～100 DEG C, and the time of described solidification is 2～24h.
The invention provides a kind of resin penetration ceramic composite, described composite is by ceramic body and permeates in institute
Stating the solidification of the hybrid resin in the porous network structure of ceramic body to form, described ceramic body has the network structure of porous,
Described ceramic body includes that the tetragonal phase zirconium oxide of stabilized with yttrium oxide, described hybrid resin include methyl acrylic ester compound
Mixture and thermal curing agents.The resin penetration ceramic composite that the present invention provides is with the ceramic network structure of porous and infiltration
Resin in ceramic network structure is constituted, and using pottery as matrix, is prevented effectively from composite volume in sintering process
Change, and then overcome the shrinkage of conventional particles toughened resin based composites, it is easy to introduce the defect of residual stress；With
The hybrid resin of the form of infiltration can fully occupy the network structure of ceramic body porous, plays the toughness reinforcing spy of hybrid resin
Property, and avoid hybrid resin that change in volume occurs in the curing process as matrices of composite material；Resin penetration pottery, ingenious
Make use of two kinds of network structures mutually run through, i.e. resin network structure, ceramic network structure, this structure overcomes resin
The cure shrinkage defect of based composites, and can effectively improve the mechanical property of composite.Embodiments of the invention
Result shows, the resin penetration composite that the present invention provides, and has higher bending strength, fracture toughness, has relatively simultaneously
Low consistency and elasticity modulus, is a class novel gear division repair composite material with broad prospect of application.
Present invention also offers the preparation method of composite described in technique scheme, the preparation side that the present invention provides
Method, is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtain hybrid resin, oozed by hybrid resin subsequently
Thoroughly in ceramic body, obtaining being impregnated with the pottery of resin, by the way of infiltration, hybrid resin can be formed and ceramic network
The resin network structure that structure runs through mutually, the resin network structure that the ceramic network structure of sintering combines therethrough constitutes tool
There is the ceramic matric composite of excellent mechanical performance, and effectively overcome the cure shrinkage performance of polymer matrix composites.
The zirconium oxide in ceramic size is made to mix homogeneously with iron sesquioxide it addition, grind；By once suppressing, it is possible to really
Protect the biscuit of ceramics obtaining certain size, suppress in conjunction with secondary, improve the compactness of biscuit of ceramics further, it is simple to resin
Infiltration, makes full use of ceramic network structure and resin network structure, and then improves follow-up obtained resin penetration Ceramic Composite material
The mechanical property of material；By sintering, preparation has the porous network structure of some strength；Mixing of methyl acrylic ester compound
Compound proportionally mix homogeneously, adds benzoyl peroxide, by the addition of benzoyl peroxide, colourless mixed solution by
Fade to faint yellow, reach to improve the aesthetic properties of resin penetration composite.
Accompanying drawing explanation
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.
Fig. 1 is the XRD spectra of ceramic body in embodiment of the present invention 1-4 resin penetration ceramic composite preparation process；
Fig. 2 is the SEM figure of ceramic body in embodiment of the present invention 1-4 resin penetration ceramic composite preparation process；
The sample photo of the resin penetration ceramic composite that Fig. 3 provides for embodiment of the present invention 5-8；
Fig. 4 is the SEM figure of ceramic body in embodiment of the present invention 5-8 resin penetration ceramic composite preparation process.
Detailed description of the invention
The invention provides a kind of resin penetration ceramic composite, described composite is by ceramic body and permeates in institute
Stating the solidification of the hybrid resin in the porous network structure of ceramic body to form, described ceramic body has the network structure of porous,
Described ceramic body includes that the tetragonal phase zirconium oxide of stabilized with yttrium oxide, described hybrid resin include methyl acrylic ester compound
Mixture and thermal curing agents.
The resin penetration ceramic composite that the present invention provides, ceramic network structure and infiltration with porous are at ceramic network
Resin in structure is constituted, and using pottery as matrix, is prevented effectively from composite change in volume in sintering process, Jin Erke
Take the shrinkage of conventional particles toughened resin based composites, it is easy to introduce the defect of residual stress.
The resin penetration ceramic composite that the present invention provides, including ceramic body, described ceramic body has porous
Network structure, heretofore described ceramic body aperture is preferably 1～3 μm, and the space of described ceramic body is uniformly distributed；Described
Ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, i.e. 3Y-TZP.The present invention does not has spy to the source of described 3Y-TZP
Different requirement, uses 3Y-TZP well-known to those skilled in the art；In an embodiment of the present invention, 3Y-TZP can be used
Commercial goods, it is possible to use the technical scheme of the 3Y-TZP of preparation well known to those skilled in the art to prepare voluntarily.In the present invention
Embodiment in, described 3Y-TZP is purchased from Tokyo Dong Cao company (Tosoh Co., Tokyo, Japan).
In the present invention, described ceramic body the most also includes iron sesquioxide, iron sesquioxide in described ceramic body
Molar percentage is preferably 0～2mol%, more preferably 0.1～1.9mol%, and can be concrete in embodiments of the invention
For 0.1mol%, 0.2mol%, 0.3mol%, 0.5mol%, 0.8mol%, 1.2mol%, 1.5mol% or 1.8mol%.
The resin penetration ceramic composite that the present invention provides, including permeating the porous network structure at described ceramic body
In hybrid resin, described hybrid resin includes mixture and the thermal curing agents of methyl acrylic ester compound.In the present invention
In, described thermal curing agents is preferably benzoyl peroxide, and the mass fraction of the described thermal curing agents in hybrid resin is preferably 0.5
～2%, more preferably 0.8～1.5%.In the embodiment of the present invention, the matter of the described thermal curing agents in described hybrid resin
Amount mark can be specially 1.0%, 1.2%, 1.4%, 1.6% or 1.8%.
In the present invention, the mixture of described methyl acrylic ester compound is preferably bisphenol-A glycerol dimethyl allene
One or more in acid esters, three (ethylene glycol) dimethylacrylate, methacrylate and polymethyl methacrylate；This
In invention, when the mixture of methyl acrylic ester compound is bisphenol-A glycerine dimethacrylate and three (ethylene glycol) two
During methacrylate, described bisphenol-A glycerine dimethacrylate and the matter of described three (ethylene glycol) dimethylacrylate
Amount ratio preferably 1:1～1:1.5, can be specially 1:1.2,1:1.3 or 1:1.4 in the embodiment of the present invention.
The invention provides the preparation method of a kind of resin penetration ceramic composite, comprise the following steps:
(1), it is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtain hybrid resin；
(2), the hybrid resin that described step (1) obtains is infiltrated in ceramic body, obtain being impregnated with the pottery of resin；
(3), the pottery being impregnated with resin that described step (2) obtains is solidified, obtain resin penetration Ceramic Composite
Material.
In the present invention, the mixture of described thermal curing agents with described methyl acrylic ester compound is mixed,
Obtain hybrid resin standby.The present invention does not has particular/special requirement to described mixed process, uses well-known to those skilled in the art
Hybrid mode；The mixture of the most described thermal curing agents and described methyl acrylic ester compound
Hybrid mode can be specially the mode of normal agitation or magnetic agitation, to described normal agitation or the speed of described magnetic agitation
There is no particular/special requirement.
In the present invention, the mixture of described methyl acrylic ester compound is preferably bisphenol-A glycerol dimethyl allene
One or more in acid esters, three (ethylene glycol) dimethylacrylate, methacrylate and polymethyl methacrylate；This
In invention, when the mixture of methyl acrylic ester compound is bisphenol-A glycerine dimethacrylate and three (ethylene glycol) two
During methacrylate, described bisphenol-A glycerine dimethacrylate and the matter of described three (ethylene glycol) dimethylacrylate
Amount ratio preferably 1:1～1:1.5, can be specially 1:1.2,1:1.3 or 1:1.4 in the embodiment of the present invention.
In the present invention, described thermal curing agents is preferably benzoyl peroxide, the described thermal curing agents in hybrid resin
Mass fraction is preferably 0.5～2%, and more preferably 0.8～1.5%.In the embodiment of the present invention, in described hybrid resin
The mass fraction of described thermal curing agents can be specially 1.0%, 1.2%, 1.4%, 1.6% or 1.8%.
The preparation method of described ceramic body preferably includes following steps:
A, by the tetragonal phase zirconium oxide of stabilized with yttrium oxide pottery and iron sesquioxide mixing, obtain mixed material；
B, the mixed material that described step a obtains is ground, obtains presoma powder body；
C, the presoma powder body described step b obtained once are suppressed, and obtain biscuit of ceramics precursor；
D, the biscuit of ceramics precursor described step c obtained carry out secondary compacting, obtain biscuit of ceramics；
E, the biscuit of ceramics that described step d obtains is sintered, obtains ceramic body.
The tetragonal zircite ceramic of stabilized with yttrium oxide is preferably mixed by the present invention with iron sesquioxide, obtains mixed material.
The present invention does not has particular/special requirement to the mode of described mixing, uses hybrid mode well-known to those skilled in the art, this
Described in inventive embodiments, the mode of mixing can be specially the mode of magnetic agitation.In the present invention, iron sesquioxide is in mixing
Molar percentage in material is preferably 0～2mol%, and more preferably 0.1～1.9mol%, in embodiments of the invention
Can be specially 0.1mol%, 0.2mol%, 0.3mol%, 0.5mol%, 0.8mol%, 1.2mol%, 1.5mol% or
1.8mol%.On the one hand the addition of iron sesquioxide of the present invention, can make the color of the color of composite and natural tooth more
For close, there is more preferable aesthetic properties, on the other hand can improve the mechanical property of composite.
After obtaining mixed material, described mixed material is preferably ground by the present invention, obtains precursor powder.At this
In bright, the mode of grinding is preferably wet grinding, and the medium of described wet grinding is preferably ethanol, and the present invention does not has spy to the addition of ethanol
Different requirement, adds wet grinding media consumption well-known to those skilled in the art；The rotating speed of grinding of the present invention is preferably
250～500rpm, more preferably 300～450rmp；In the present invention, the time of described grinding is preferably 2～24h, enters
One step is preferably 5～20h.In the present invention, after completing the grinding to described mixed material, the particle diameter of precursor powder is preferably
50～100 mesh, more preferably 60～80 mesh.
After obtaining precursor powder, described presoma powder body is once suppressed by the present invention, obtains biscuit of ceramics
Precursor.When in the present invention without iron sesquioxide, preferably the tetragonal zircite ceramic of stabilized with yttrium oxide is directly carried out one
Secondary compacting, obtains biscuit of ceramics precursor.In the present invention before described once compacting, preferably described precursor powder is done
Dry.In the present invention, the described dry time is preferably 2～24h, and more preferably 10～15h；Described dry temperature is excellent
Elect 50～80 DEG C as, more preferably 55～75 DEG C.
The present invention does not has special restriction to the described equipment once suppressing employing, uses well known to those skilled in the art
Tablet machine.In the present invention, the described pressure once suppressed is preferably 2～10MPa, more preferably 3.5～
7.5MPa；In the present invention, the described dwell time once suppressed is preferably 2～4min, once suppresses in the embodiment of the present invention
Dwell time can be specially 2.5min, 3min or 3.5min.
After obtaining biscuit of ceramics precursor, described biscuit of ceramics precursor is carried out secondary compacting by the present invention, obtains comparatively dense
Biscuit of ceramics.In the present invention, the compacting of described secondary uses the mode of isostatic cool pressing well-known to those skilled in the art, institute
The pressure stating secondary compacting is preferably 150～220MPa, and more preferably 180～200MPa；In the present invention, described secondary
Compacting dwell time be preferably 0.5～3min, the dwell time once suppressed in the embodiment of the present invention can be specially 1.0min,
1.5min or 2min.
After obtaining the biscuit of ceramics of secondary compacting, described biscuit of ceramics is preferably sintered by the present invention, obtains ceramic blank
Body.In the present invention, sintering preferably partially sinters mode, present invention preferably employs well-known to those skilled in the art and complete
Corresponding the partially sintering of dense sintering, less than the temperature of complete dense sintering.In the present invention, the temperature of described sintering is preferred
It is 1000～1150 DEG C, the embodiment of the present invention can be specially 1050 DEG C, 1080 DEG C, 1100 DEG C or 1120 DEG C；In the present invention,
The time of described sintering is preferably 2～4h, in an embodiment of the present invention, can be specially 2.5h, 2.7h, 2.9h, 3.0h, 3.2h
Or 3.5h.The present invention does not has particular/special requirement to sintering atmosphere, uses sintering atmosphere well-known to those skilled in the art, this
In inventive embodiments, sintering atmosphere is sintered under can being specially air atmosphere.
After the present invention obtains ceramic body, the hybrid resin described in technique scheme is infiltrated into described ceramic body
In, obtain being impregnated with the pottery of resin.In the present invention, it is preferred to use the mode of vacuum infiltration to permeate, described vacuum is oozed
Saturating vacuum is preferably-0.1MPa；In the present invention, the time of described infiltration is preferably 2～24h, more preferably 5～
20h；In embodiments of the present invention, 8h, 10h, 12h, 14h, 16h or 18h can be specially.
The described pottery being impregnated with resin, through infiltration, after obtaining being impregnated with the pottery of resin, is solidified by the present invention,
Obtain resin penetration ceramic composite.In the present invention, the temperature of described solidification is preferably 50～100 DEG C, further preferably
It is 60～85 DEG C, most preferably 65～75 DEG C；The time of described solidification is preferably 2～24h, and more preferably 5～20h,
It is preferably 10～15h.In the present invention, it is preferred to use the mode of vacuum solidification to solidify, the embodiment of the present invention is specifically adopted
It is used in the mode carrying out solidifying in vacuum drying oven well-known to those skilled in the art.
The invention provides a kind of resin penetration ceramic composite, described composite is by ceramic body and permeates in institute
Stating the solidification of the hybrid resin in the porous network structure of ceramic body to form, described ceramic body has the network structure of porous,
Described ceramic body includes that the tetragonal phase zirconium oxide of stabilized with yttrium oxide, described hybrid resin include methyl acrylic ester compound
Mixture and thermal curing agents.The resin penetration ceramic composite that the present invention provides is with the ceramic network structure of porous and infiltration
Resin in ceramic network structure is constituted, and using pottery as matrix, is prevented effectively from composite volume in sintering process
Change, and then overcome the shrinkage of conventional particles toughened resin based composites, it is easy to introduce the defect of residual stress；With
The hybrid resin of the form of infiltration can fully occupy the network structure of ceramic body porous, plays the toughness reinforcing spy of hybrid resin
Property, and avoid hybrid resin as the cure shrinkage occurred during the matrix of composite；Resin penetration pottery, utilizes dexterously
Two kinds of network structures mutually run through, i.e. resin network structure, ceramic network structure, this structure overcomes resin base and is combined
The cure shrinkage defect of material, and can effectively improve the mechanical property of composite.
Present invention also offers the preparation method of composite described in technique scheme, the preparation side that the present invention provides
Method, is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtain hybrid resin, oozed by hybrid resin subsequently
Thoroughly in ceramic body, obtaining being impregnated with the pottery of resin, by the way of infiltration, hybrid resin can be formed and ceramic network
The resin network structure that structure runs through mutually, the resin network structure that the ceramic network structure of sintering combines therethrough constitutes tool
There is the ceramic matric composite of excellent mechanical performance, and effectively overcome the cure shrinkage performance of polymer matrix composites.
The zirconium oxide in ceramic size is made to mix homogeneously with iron sesquioxide it addition, grind；By once suppressing, it is possible to really
Protect the biscuit of ceramics obtaining certain size, suppress in conjunction with secondary, improve the compactness of biscuit of ceramics further, it is simple to resin
Infiltration, makes full use of ceramic network structure and resin network structure, and then improves follow-up obtained resin penetration Ceramic Composite material
The mechanical property of material；By sintering, preparation has the porous network structure of some strength；Mixing of methyl acrylic ester compound
Compound proportionally mix homogeneously, adds benzoyl peroxide, by the addition of benzoyl peroxide, colourless mixed solution by
Fade to faint yellow, reach to improve the aesthetic properties of resin penetration composite.
Carry out in detail below in conjunction with resin penetration ceramic composite that the present invention is provided by embodiment and preparation method thereof
Explanation, but they can not be interpreted as limiting the scope of the present invention.
In following example, the method for the mechanics properties testing of gained sample is as follows: utilize universal testing machine according to
The bending strength of ISO4049 standardized test specimen and fracture toughness.Bending strength is tested, with gold steel blade by resin penetration
Zirconia ceramics sample is cut into 2 × 3 × 16mm3Batten, utilize afterwards abrasive pastes by sample upper and lower surface polish, each sample
Test 22 battens.For fracture toughness, with gold steel blade, resin penetration zirconia ceramics sample is cut into 2 × 4 × 16mm3's
Batten, cuts the otch of about 2mm length, 22 battens of each sample test at batten side diamant.For consistency and elasticity mould
Amount, utilizes Nanoindentation to test, after being polished by sample according to polishing technology well-known to those skilled in the art, at random
Testing 10 points, depth of cup is fixed as 500nm.
Embodiment 1
Weighing the 3Y-TZP of 4.5g, utilize tablet machine that powder is compressed to biscuit of ceramics precursor, pressure is 4MPa, during pressurize
Between be 3min；Utilizing isostatic cool pressing compacting zirconia ceramics biscuit to obtain finer and close biscuit of ceramics, pressure is 220MPa, protects
The pressure time is 1min；Biscuit of ceramics being sintered obtain ceramic body in air atmosphere standby, wherein sintering temperature is
1000 DEG C, temperature retention time is 2h.By bisphenol-A glycerine dimethacrylate that mass ratio is 1:1 and three (ethylene glycol) diformazan
Base acrylate mixes, and utilizes magnetic agitation to stir 2h；Firming agent benzoyl peroxide adds above-mentioned hybrid resin relaying
Continuous stirring 2h, obtains resin solution, and according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；By standby
Ceramic body immerses in resin solution, is placed in the vacuum environment that vacuum is-0.1MPa, permeates 4h；By the pottery of infiltration resin
Porcelain base substrate is placed in vacuum drying oven solidification, and solidification temperature is 70 DEG C, and hardening time is 2h, obtains resin penetration zirconium oxide composite wood
Material.
This embodiment preparation process sinters 1000 DEG C of corresponding SEM in the XRD figure such as Fig. 1 of the ceramic body obtained and schemes institute
Show, peak position in figure understand ceramic body and form correctly, for tetragonal phase zirconium oxide；Ceramic body in the present embodiment preparation process
SEM figure as shown in a in Fig. 2, as known in the figure owing to partially sintering, ceramic body is the network structure of porous, ceramic crystalline grain
It is about 0.1 μm.
Embodiment 1 sample in the mechanical property such as table 1 of resin penetration zirconium oxide composite material sample prepared by this embodiment
Shown in corresponding data, display bending strength is up to 121.8 ± 10.1MPa, and fracture toughness is up to 1.6 ± 0.3MPa × m1/2,
Hardness is 1.7 ± 0.2GPa, and elastic modelling quantity is 34.2 ± 2.7GPa.
Embodiment 2
Weighing the 3Y-TZP of 4.5g, utilize tablet machine that powder is compressed to biscuit of ceramics precursor, pressure is 4MPa, during pressurize
Between be 3min；Utilizing the biscuit of ceramics that isostatic cool pressing compacting zirconia ceramics biscuit obtains, wherein pressure is 220MPa, during pressurize
Between be 1min；Being sintered obtaining ceramic body in air atmosphere by ceramic body biscuit, sintering temperature is 1050 DEG C, insulation
Time is 2h.Bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylate that mass ratio is 1:1 are entered
Row mixing, utilizes magnetic agitation to stir 2h, obtains resin solution；Firming agent benzoyl peroxide is added in above-mentioned resin solution
Continuing stirring 2h, according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；Ceramic body is immersed mixing
In resin solution, it is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven solidification, solidification temperature
Being 70 DEG C, hardening time is 2h, obtains resin penetration zirconium oxide composite material.
The XRD spectra of the ceramic body that this embodiment sintering obtains is as shown in 1050 DEG C of corresponding spectrograms in Fig. 1, by this
It is correct, for tetragonal phase zirconium oxide that figure understands ceramic body composition；The present embodiment sinters the SEM figure such as figure of the ceramic body obtained
In 2 shown in b, needed for the resin penetration ceramic composite prepared by this embodiment as known in the figure, ceramic body sample is many
The network structure in hole.
Embodiment 2 sample in the mechanical property such as table 1 of resin penetration zirconium oxide composite material sample prepared by this embodiment
Shown in corresponding data, the bending strength of display sample is up to 113.1 ± 6.3MPa, and fracture toughness is up to 1.5 ± 0.4MPa
×m1/2, hardness is 1.7 ± 0.2GPa, and elastic modelling quantity is 34.2 ± 3.5GPa.
Embodiment 3
Weigh 4.5g 3Y-TZP, utilize tablet machine that powder is compressed to biscuit of ceramics precursor, pressure is 4MPa, pressurize
Time is 3min；Utilizing isostatic cool pressing compacting zirconia ceramics biscuit to obtain biscuit of ceramics, pressure is 220MPa, and the dwell time is
1min；Being sintered in air atmosphere by biscuit of ceramics, sintering temperature is 1100 DEG C, and temperature retention time is 2h, obtains ceramic blank
Body.Bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylate that mass ratio is 1:1 are mixed
Close, utilize magnetic agitation to stir 2h；Firming agent benzoyl peroxide is added in above-mentioned hybrid resin and continue stirring 2h, set
Lipoprotein solution, according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；The pottery of presintering is immersed resin
In solution, it is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven solidification, and solidification temperature is 70
DEG C, hardening time is 2h, obtains resin penetration zirconium oxide composite material.
The XRD spectra of ceramic body sample that this embodiment sintering obtains as shown in 1100 DEG C of corresponding spectrograms in Fig. 1,
Ceramic body composition is correct, for tetragonal phase zirconium oxide as known in the figure；The required pottery of the present embodiment resin penetration ceramic composite
The SEM figure of porcelain base substrate sample as shown in c in Fig. 2, the resin penetration Ceramic Composite material prepared by this embodiment as known in the figure
The required ceramic body sample of material is the network structure of porous.
Embodiment 3 sample in the mechanical property such as table 1 of resin penetration zirconium oxide composite material sample prepared by this embodiment
Shown in corresponding data, the bending strength of display sample up to 184.0 ± 9.8MPa, fracture toughness up to 2.6 ± 0.1MPa ×
m1/2, hardness is 1.9 ± 0.6GPa, and elastic modelling quantity is 44.2 ± 4.3GPa.
Embodiment 4
Weighing the 3Y-TZP of 4.5g, utilize tablet machine that powder is compressed to biscuit of ceramics precursor, pressure is 4MPa, during pressurize
Between be 3min；Utilizing isostatic cool pressing compacting zirconia ceramics biscuit precursor to obtain ceramic body, pressure is 220MPa, the dwell time
For 1min；Being sintered in air atmosphere by biscuit of ceramics, sintering temperature is 1150 DEG C, and temperature retention time is 2h.By mass ratio
Example is the bisphenol-A glycerine dimethacrylate of 1:1 and three (ethylene glycol) dimethylacrylate mixes, and utilizes magnetic force to stir
Agitating mixes 2h, obtains resin solution；Firming agent benzoyl peroxide is added in above-mentioned hybrid resin and continue stirring 2h, according to accounting for
The mass fraction meter of hybrid resin, the addition of firming agent is 1%；The pottery of presintering is immersed in resin solution, is placed in true
In Altitude, permeate 4h；The material of infiltration resin is placed in vacuum drying oven solidification, and solidification temperature is 70 DEG C, and hardening time is
2h, obtains resin penetration zirconium oxide composite material.
The XRD spectra of ceramic body sample that this embodiment sintering obtains as shown in 1150 DEG C of corresponding spectrograms in Fig. 1,
Ceramic body composition is correct, for tetragonal phase zirconium oxide as known in the figure；The SEM of the ceramic body sample that the present embodiment sintering obtains
Figure as shown in d in Fig. 2, ceramic body sample needed for the resin penetration ceramic composite prepared by this embodiment as known in the figure
Product are the network structures of porous.Shown by the SEM figure of ceramic body in Fig. 2 resin penetration ceramic composite preparation process, with
The rising of sintering temperature, the crystallite dimension change of sample is little, about 0.1 μm, but porosity is gradually reduced, and crystal boundary is gradually
Increase.
The mechanical property of sample prepared by this embodiment shown in data, shows gained as corresponding to embodiment 4 sample in table 1
The bending strength of sample is up to 240.3 ± 7.4MPa, and fracture toughness is up to 3.7 ± 0.2MPa × m1/2, hardness is 3.1 ±
0.2GPa, elastic modelling quantity is 58.8 ± 2.0GPa.
Embodiment 5
Weigh the 3Y-TZP of 4.5g, powder inserted in ball grinder, add dehydrated alcohol and carry out ball milling as ball-milling medium,
Rotational speed of ball-mill is 250rpm, and the time is 10h, obtains precursor powder；By this precursor powder in 70 DEG C of dry 24h；Use tabletting
Precursor powder is compressed to biscuit of ceramics precursor by machine, and pressure is 4MPa, and the dwell time is 3min；Isostatic cool pressing is utilized to suppress oxygen
Changing zircon ceramic biscuit precursor, pressure is 220MPa, and the dwell time is 1min, obtains biscuit of ceramics；By biscuit of ceramics at air gas
Being sintered under atmosphere, sintering temperature is 1150 DEG C, and temperature retention time is 2h.By the bisphenol-A glycerol dimethyl propylene that mass ratio is 1:1
Olefin(e) acid ester and three (ethylene glycol) dimethylacrylate mix, and utilize magnetic agitation to stir 2h, obtain resin solution；Will be solid
Agent benzoyl peroxide adds and continues stirring 2h in above-mentioned hybrid resin, according to accounting for the mass fraction meter of hybrid resin, and solidification
The addition of agent is 1%；The pottery of presintering is immersed in resin solution, is placed in vacuum environment, permeate 4h；By infiltration resin
Material be placed in vacuum drying oven solidification, solidification temperature is 70 DEG C, and hardening time is 2h, obtains resin penetration zirconium oxide composite wood
Material.
The photo of the sintering ceramic body sample that this embodiment obtains is as shown in a in Fig. 3, and its color is white as known in the figure
Chalk color, differs farther out with natural color of teeth；The present embodiment sintering ceramic body sample SEM spectrogram as shown in a and b in Fig. 4,
Needed for the resin penetration ceramic composite prepared by this embodiment as known in the figure, ceramic body sample is the network of porous
Structure.
In the mechanical property table 2 of sample prepared by this embodiment shown in data corresponding to embodiment 5 gained sample, display
1150 DEG C of sintering temperatures, do not adulterate Fe2O3, the bending strength of gained sample is up to 240.3 ± 7.4MPa, and fracture toughness can
Reach 3.7 ± 0.2MPa × m1/2, hardness is 3.1 ± 0.2GPa, and elastic modelling quantity is 58.8 ± 2.0GPa.
Embodiment 6
Weigh 3Y-TZP and Fe2O34.5g, wherein Fe altogether2O3Content 0.1mol%, inserts powder in ball grinder, adds
Dehydrated alcohol carries out ball milling as ball-milling medium, and rotational speed of ball-mill is 250rpm, and the time is 10h, obtains precursor powder；Before this
Drive body powder in 70 DEG C of dry 24h；With tablet machine, precursor powder being compressed to biscuit of ceramics precursor, pressure is 4MPa, pressurize
Time is 3min；Utilizing isostatic cool pressing to suppress zirconia ceramics biscuit precursor, pressure is 220MPa, and the dwell time is 1min,
To biscuit of ceramics；Being sintered in air atmosphere by biscuit of ceramics, wherein sintering temperature is 1150 DEG C, and temperature retention time is that 2h obtains
To ceramic body.By bisphenol-A glycerine dimethacrylate that mass ratio is 1:1 and three (ethylene glycol) dimethylacrylate
Mix, utilize magnetic agitation to stir 2h, obtain resin solution；Firming agent benzoyl peroxide is added above-mentioned hybrid resin
Middle continuing stirring 2h, according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；Ceramic body is immersed tree
In lipoprotein solution, it is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven solidification, and solidification temperature is
70 DEG C, hardening time is 2h, obtains resin penetration zirconium oxide composite material.
The photo of the sample of the sintered body that this embodiment obtains is as shown in b in Fig. 3, and its color is yellowish as known in the figure
Color, is close with natural color of teeth；Needed for the present embodiment resin penetration ceramic composite, the SEM of ceramic body schemes such as Fig. 4
Shown in middle c and d, needed for the resin penetration ceramic composite prepared by this embodiment as known in the figure, ceramic body sample is
The network structure of porous.
Shown in the data that the mechanical property of sample prepared by this embodiment is as corresponding in embodiment 6 gained sample in table 2, result
Showing, sinter through 1150 DEG C of temperature, adulterate 0.1mol%Fe2O3The bending strength of situation gained sample up to 242.6 ±
10MPa, fracture toughness is up to 3.8 ± 0.2MPa × m1/2, hardness is 4.0 ± 0.6GPa, and elastic modelling quantity is 72.3 ± 6.4GPa.
Embodiment 7
Weigh 3Y-TZP and Fe2O34.5g, wherein Fe altogether2O3Content is 0.2mol%, is inserted by powder in ball grinder, adds
Entering dehydrated alcohol and carry out ball milling as ball-milling medium, rotational speed of ball-mill is 250rpm, and the time is 10h, obtains precursor powder；Should
Precursor powder is in 70 DEG C of dry 24h；With tablet machine, precursor powder being compressed to biscuit of ceramics precursor, pressure is 4MPa, protects
The pressure time is 3min；Utilizing isostatic cool pressing to suppress zirconia ceramics biscuit precursor, pressure is 220MPa, and the dwell time is 1min,
Obtain biscuit of ceramics；Being sintered in air atmosphere by biscuit of ceramics, wherein sintering temperature is 1150 DEG C, and temperature retention time is
2h, obtains ceramic body.By bisphenol-A glycerine dimethacrylate that mass ratio is 1:1 and three (ethylene glycol) dimethyl propylene
Olefin(e) acid ester mixes, and utilizes magnetic agitation to stir 2h, obtains resin solution；Firming agent benzoyl peroxide is added above-mentioned tree
Continuing stirring 2h in lipoprotein solution, according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；By ceramic body
Immerse in resin solution, be placed in vacuum environment, permeate 4h；The material of infiltration resin is placed in vacuum drying oven solidification, solidification
Temperature is 70 DEG C, and hardening time is 2h, obtains resin penetration zirconium oxide composite material.
The photo of resin penetration zirconium oxide composite material sample prepared by this embodiment is as shown in c in Fig. 3, as known in the figure
Its color is faint yellow, is close with natural color of teeth；Ceramic body needed for the present embodiment resin penetration ceramic composite
SEM figure as shown in e and f in Fig. 4, in the present embodiment, needed for resin penetration ceramic composite, ceramic body is as known in the figure
The network structure of porous.
In the mechanical property table 2 of sample prepared by this embodiment shown in data corresponding to embodiment 7 gained sample, result
Showing sintering temperature 1150 DEG C, adulterate 0.1mol%Fe2O3The bending strength of gained sample is up to 336.8 ± 12.7MPa, disconnected
Split toughness up to 3.9 ± 0.3MPa × m1/2, hardness is 4.7 ± 0.3GPa, and elastic modelling quantity is 88.2 ± 3.7GPa.
Embodiment 8
Weigh 3Y-TZP and Fe2O34.5g, Fe altogether2O3Content 0.3mol%, inserts powder in ball grinder, adds anhydrous
Ethanol carries out ball milling as ball-milling medium, and rotational speed of ball-mill is 250rpm, and the time is 10h, obtains precursor powder；By this presoma
Powder is in 70 DEG C of dry 24h；With tablet machine, precursor powder being compressed to biscuit of ceramics precursor, pressure is 4MPa, the dwell time
For 3min；Utilizing isostatic cool pressing to suppress zirconia ceramics biscuit precursor, pressure is 220MPa, and the dwell time is 1min, is made pottery
Porcelain biscuit；Being sintered in air atmosphere by biscuit of ceramics, sintering temperature is 1150 DEG C, and temperature retention time is that 2h obtains ceramic blank
Body.Bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylate that mass ratio is 1:1 are mixed
Close, utilize magnetic agitation to stir 2h, obtain resin solution；Firming agent benzoyl peroxide is added in above-mentioned hybrid resin and continues
Stirring 2h, according to accounting for the mass fraction meter of hybrid resin, the addition of firming agent is 1%；Ceramic body is immersed resin solution
In, it is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven solidification, and solidification temperature is 70 DEG C, Gu
The change time is 2h, obtains resin penetration zirconium oxide composite material.
The photo of the sample of resin penetration zirconium oxide composite material prepared by this embodiment, can by this figure as shown in d in Fig. 3
Know that its color is faint yellow, be close with natural color of teeth；Ceramic blank needed for the present embodiment resin penetration ceramic composite
The SEM figure of body, as shown in g and h in Fig. 4, sinters the resin penetration ceramic composite obtained as known in the figure by this embodiment
Required ceramic body sample is the network structure of porous.By ceramic body in Fig. 4 resin penetration ceramic composite preparation process
SEM figure shown in, along with the rising of sintering temperature, the crystallite dimension change of sample is little, about 0.1 μm, but porosity by
The least, crystal boundary gradually increases.
The mechanical property of sample prepared by this embodiment shown in data, is adulterated as corresponding to embodiment 8 gained sample in table 2
0.3mol%Fe2O3Through 1150 DEG C of bending strengths sintering gained samples up to 370.9 ± 15.1MPa, fracture toughness is up to 5.4
±0.4MPa×m1/2, hardness is 8.0 ± 0.4GPa, and elastic modelling quantity is 129.3 ± 10.5GPa.
Table 1 is through the mechanical property of different sintering temperature gained resin penetration ceramic composites
As can be seen from Table 1, the resin penetration ceramic composite excellent in mechanical performance prepared, bending strength, disconnected
Split toughness, elastic modelling quantity and hardness number the highest；When sintering temperature is 1000 DEG C, 1050 DEG C and 1100 DEG C, bending strength,
Fracture toughness, elastic modelling quantity and hardness are not clearly distinguished from, when sintering temperature reaches 1150 DEG C, and bending strength, fracture
Toughness, elastic modelling quantity and hardness all have and improve greatly.
The mechanical property of table 2 iron sesquioxide difference doping gained resin penetration ceramic composite
As can be seen from Table 2, the resin penetration ceramic composite excellent in mechanical performance prepared, bending strength, disconnected
Split toughness, elastic modelling quantity and hardness number the highest；Along with the increase of iron sesquioxide doping, the resin penetration prepared
The bending strength of ceramic composite, fracture toughness, elastic modelling quantity and hardness all gradually rise.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a resin penetration ceramic composite, described composite is many at described ceramic body by ceramic body and infiltration
Hybrid resin solidification in pore network structure forms, and described ceramic body has the network structure of porous, described ceramic body bag
Including the tetragonal phase zirconium oxide of stabilized with yttrium oxide, described hybrid resin includes mixture and the thermosetting of methyl acrylic ester compound
Agent.
Composite the most according to claim 1, it is characterised in that described ceramic body also includes iron sesquioxide, institute
State iron sesquioxide in ceramic body molar percentage be 0～3mol%.
Composite the most according to claim 1, it is characterised in that described thermal curing agents is benzoyl peroxide.
Composite the most according to claim 1, it is characterised in that the mixture of described methyl acrylic ester compound
For bisphenol-A glycerine dimethacrylate, three (ethylene glycol) dimethylacrylate, methacrylate and polymethylacrylic acid
One or more of methyl ester.
5. a preparation method for the resin penetration ceramic composite described in Claims 1 to 4 any one, including following step
Rapid:
(1), it is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtain hybrid resin；
(2), the hybrid resin that described step (1) obtains is infiltrated in ceramic body, obtain being impregnated with the pottery of resin；
(3), the pottery being impregnated with resin that described step (2) obtains is solidified, obtain resin penetration ceramic composite.
Preparation method the most according to claim 5, it is characterised in that the preparation method of described ceramic body includes following step
Rapid:
A, by the tetragonal phase zirconium oxide of stabilized with yttrium oxide pottery and iron sesquioxide mixing, obtain mixed material；
B, the mixed material that described step a obtains is ground, obtains presoma powder body；
C, the presoma powder body described step b obtained once are suppressed, and obtain biscuit of ceramics precursor；
D, the biscuit of ceramics precursor described step c obtained carry out secondary compacting, obtain biscuit of ceramics；
E, the biscuit of ceramics that described step d obtains is sintered, obtains ceramic body.
Preparation method the most according to claim 5, it is characterised in that the mass fraction of thermal curing agents in described hybrid resin
It is 0.5～2%.
Preparation method the most according to claim 5, it is characterised in that the time of the infiltration described in step (2) is 2～24h.
Preparation method the most according to claim 5, it is characterised in that the environment of the infiltration described in step (2) is vacuum ring
Border.
Preparation method the most according to claim 5, it is characterised in that the temperature of step (3) described solidification is 50～100
DEG C, the time of described solidification is 2～24h.
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| CN115894001B (en) * | 2023-03-10 | 2023-05-09 | 湖南康纳新材料有限公司 | High-hardness wear-resistant resin-infiltrated ceramic composite material and preparation method and application thereof |
| CN116698632A (en) * | 2023-07-20 | 2023-09-05 | 龙华相位新材料(绵阳)股份有限公司 | Method for testing folding endurance of optical film |
| CN116698632B (en) * | 2023-07-20 | 2023-11-03 | 龙华相位新材料(绵阳)股份有限公司 | Method for testing folding endurance of optical film |
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